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Ruthenium(II)−Bipyridine/NanoC 3 N 4 Hybrids: Tunable Photochemical Properties by Using Exchangeable Alkali Metal Cations
Author(s) -
Mori Kohsuke,
Tatsumi Daisuke,
Iwamoto Tomoyuki,
Masui Yoichi,
Onaka Makoto,
Yamashita Hiromi
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201800397
Subject(s) - ruthenium , alkali metal , metal , chemistry , bipyridine , photochemistry , inorganic chemistry , 2,2' bipyridine , crystallography , catalysis , organic chemistry , crystal structure
A series of nanoporous carbon nitrides that contained a range of alkali metal cations (M@nanoC 3 N 4 : M=Li + , Na + , K + , Rb + , and Cs + ) have been successfully synthesized from as‐synthesized g‐C 3 N 4 by delamination with concentrated sulfuric acid, followed by neutralization with aqueous solutions of the corresponding alkali metal hydroxides. Tris(2,2′‐bipyridine)ruthenium(II) complexes, [Ru(bpy) 3 ] 2+ , were grafted onto the carbon nitrides in an effort to explore the physicochemical properties of the deposited [Ru(bpy) 3 ] 2+ , as well as its photocatalytic activity in the aerobic photooxidation of phenylboronic acid and H 2 production from aqueous media in the presence of a Pt co‐catalyst under visible‐light irradiation. Highly porous nanoC 3 N 4 could significantly enhance photocatalytic activity, because of its high surface area, owing to its unique porous structure. More interestingly, the photoluminescence intensities of [Ru(bpy) 3 ] 2+ complexes that were associated with M@nanoC 3 N 4 increased in the presence of lighter alkali metal cations, which correlated with increased photocatalytic activities for both reactions. This study demonstrates that M@nanoC 3 N 4 are fascinating supports, in which the local environment of an immobilized metal complex can be precisely controlled by varying the alkali metal cation from Li + to Cs + .